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The Role of Conjugation in the Halogen−Lithium Exchange Selectivity: Lithiation of 4,6,7,9‐Tetrabromo‐1,3‐dimethyl‐2,3‐dihydro‐1H‐perimidine
Yakubenko, Artyom A.
, Tupikina, Elena Yu.
and Antonov, Alexander S.
(2023)
The Role of Conjugation in the Halogen−Lithium Exchange Selectivity: Lithiation of 4,6,7,9‐Tetrabromo‐1,3‐dimethyl‐2,3‐dihydro‐1H‐perimidine.
Chemistry – A European Journal.
Date of publication of this fulltext: 26 Jul 2023 04:55
Article
DOI to cite this document: 10.5283/epub.54521
Abstract
The first case of successful suppression of the coordination of a lithium atom with a dialkylamino group by the effective conjugation of the latter with the aromatic core has been discovered. This effect controls regioselectivity of the bromine-lithium exchange in 4,6,7,9-tetrabromo-1,3-dimethyl-2,3-dihydro-1H-perimidine, which leads to products with the most effective conjugation. As a result, ...
The first case of successful suppression of the coordination of a lithium atom with a dialkylamino group by the effective conjugation of the latter with the aromatic core has been discovered. This effect controls regioselectivity of the bromine-lithium exchange in 4,6,7,9-tetrabromo-1,3-dimethyl-2,3-dihydro-1H-perimidine, which leads to products with the most effective conjugation. As a result, the product of this quadruple exchange demonstrates no tendency of the coordination of the NMe groups to neighboring lithium atoms despite the absence of steric restrictions. Experimental results are explained by means of quantum chemical calculations: geometry optimization, natural bond analysis and scans using the modredundant scheme.
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| Item type | Article | ||||
| Journal or Publication Title | Chemistry – A European Journal | ||||
| Publisher: | WILEY-V C H VERLAG GMBH | ||||
|---|---|---|---|---|---|
| Place of Publication: | WEINHEIM | ||||
| Date | 1 June 2023 | ||||
| Institutions | Chemistry and Pharmacy > Institut für Organische Chemie | ||||
| Identification Number |
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| Keywords | ; organolithiums; conjugation; coordination; regioselectivity; naphthalene | ||||
| Dewey Decimal Classification | 500 Science > 540 Chemistry & allied sciences | ||||
| Status | Published | ||||
| Refereed | Yes, this version has been refereed | ||||
| Created at the University of Regensburg | Partially | ||||
| URN of the UB Regensburg | urn:nbn:de:bvb:355-epub-545215 | ||||
| Item ID | 54521 |
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